EP0040171A2 - Colorants azoiques, procédé pour leur préparation et leur utilisation dans les matériaux photographiques en couleurs pour le procédé de blanchiment à l'argent - Google Patents

Colorants azoiques, procédé pour leur préparation et leur utilisation dans les matériaux photographiques en couleurs pour le procédé de blanchiment à l'argent Download PDF

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Publication number
EP0040171A2
EP0040171A2 EP81810154A EP81810154A EP0040171A2 EP 0040171 A2 EP0040171 A2 EP 0040171A2 EP 81810154 A EP81810154 A EP 81810154A EP 81810154 A EP81810154 A EP 81810154A EP 0040171 A2 EP0040171 A2 EP 0040171A2
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EP
European Patent Office
Prior art keywords
carbon atoms
optionally substituted
alkyl
hydrogen
cyano
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Granted
Application number
EP81810154A
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German (de)
English (en)
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EP0040171A3 (en
EP0040171B1 (fr
Inventor
John Dr. Lenoir
Gérald Dr. Jan
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Novartis AG
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Ciba Geigy AG
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Publication of EP0040171A3 publication Critical patent/EP0040171A3/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
    • C09B29/08—Amino benzenes
    • C09B29/0833—Amino benzenes characterised by the substituent on the benzene ring excepted the substituents: CH3, C2H5, O-alkyl, NHCO-alkyl, NHCOO-alkyl, NHCO- C6H5, NHCOO-C6H5
    • C09B29/0836—Amino benzenes characterised by the substituent on the benzene ring excepted the substituents: CH3, C2H5, O-alkyl, NHCO-alkyl, NHCOO-alkyl, NHCO- C6H5, NHCOO-C6H5 linked through -N=
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
    • C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
    • C09B29/3604—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom
    • C09B29/3617—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom
    • C09B29/3643—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom from quinolines or hydrogenated quinolines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
    • C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
    • C09B29/3686—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing nitrogen and oxygen as heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
    • C09B31/02—Disazo dyes
    • C09B31/04—Disazo dyes from a coupling component "C" containing a directive amino group
    • C09B31/043—Amino-benzenes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/28—Silver dye bleach processes; Materials therefor; Preparing or processing such materials
    • G03C7/29—Azo dyes therefor
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S534/00—Organic compounds -- part of the class 532-570 series
    • Y10S534/02—Azo compounds containing chains of eight or more carbon atoms not provided for elsewhere in this class

Definitions

  • the present invention relates to new azo dyes, a process for their preparation and the use of these compounds as image dyes in photographic silver color bleaching materials.
  • the object of the present invention is to provide new azo dyes for photographic silver color bleaching materials.
  • the invention further relates to a method for producing the azo dyes according to the invention. This process makes the product of formula (1) accessible in high yield and purity.
  • the invention further relates to the use of the azo dyes according to the invention as image dyes in photographic silver color bleaching materials, the photographic material containing these dyes, its production, its use for the production of photographic images and the images produced therewith.
  • Another object of the invention relates to the use of the azo dyes according to the invention for dyeing textile materials.
  • the substituents X and X 2 which are part of the ester group, can independently of one another be alkyl having 1 to 24 carbon atoms, in particular having 1 to 18 carbon atoms, where the alkyl radicals can be straight-chain or branched, such as methyl, ethyl, propyl, i- Propyl, butyl, i-butyl, tert.
  • alkyl radicals can be substituted with hydroxyl, alkoxy with 1 to 4 carbon atoms, especially methoxy, cyano or phenyl.
  • Halogen such as fluorine, chlorine or bromine, are suitable as further substituents.
  • X 1 and X 2 may furthermore mean alkenyl having 2 to 4 carbon atoms such as ethenyl or propenyl or optionally substituted cycloalkyl having 5 or 6 carbon atoms, such as, for example, cyclopentyl or cyclohexyl.
  • the substituents X 1 and X 2 is optionally substituted aralkyl having from 1 to 4 carbon atoms in the alkyl part or optionally substituted aryl, such benzyl and phenyl are particularly suitable groups.
  • Hydrogen or alkyl having 1 to 5 carbon atoms are suitable for the substituent Y.
  • the alkyl radicals can be either straight-chain or branched. You can e.g. Methyl, ethyl, propyl, i-propyl, butyl, i-butyl, tert. Butyl, amyl or tert. Represent amyl (1,1-dimethylpropyl).
  • a suitable substituent for these radicals is alkoxy having 1 to 4 carbon atoms, in particular methoxy and ethoxy, and also hydroxyl and cyano.
  • the substituent Y 2 which is in the geminal position to Y 1 denotes hydrogen, alkyl having 1 to 12 carbon atoms, preferably having 1 to 8 carbon atoms;
  • the alkyl radicals Y 2 can be the same as those already indicated for Y 1 .
  • hexyl, 1-methylpentyl or neopentyl are also possible, and 1-, 2- or 3-methylhexyl, heptyl, n-octyl, tert.-octyl, 2-ethylhexyl, n-nonyl, isononyl, tert.
  • Alkyl substituents are, for example, hydroxyl, methoxy, phenyl, halogen such as fluorine, chlorine or bromine, cyano or U 1 -CO-, where U 1 is hydrogen, alkyl or alkoxy each having 1 to 6 carbon atoms or phenyl.
  • the preferred meaning of U l -CO- is formyl, acetyl or benzoyl.
  • acyloxy groups such as, for example, come into question.
  • the alkyl radicals in this acyloxy group contain 1 to 6, preferably 1 or 2, carbon atoms.
  • Preferred aryl radicals are phenyl and, for example, phenyl substituted with chlorine, bromine, cyano or nitro.
  • Y 2 is also alkenyl having 2 to 4 carbon atoms. If the substituent Y 2 is aryl, it can be substituted by alkyl or alkoxy each having 1 to 5 carbon atoms or chlorine. It is preferred in the meaning of phenyl.
  • Both substituents Y 1 and Y 2 together with the nitrogen atom to which they are attached can form 5- or 6-membered rings, for example Saturated 5-membered rings such as pyrro are particularly suitable Lidin remnants.
  • a substituent on these rings is, for example, carbalkoxy having 2 to 5 carbon atoms, in particular having 2 or 3 carbon atoms.
  • the substituent Z is alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 5 carbon atoms.
  • the alkyl radicals are the same as those already given for Y 1 .
  • Suitable alkoxy radicals are the radicals analogous to the alkyl radicals mentioned. In both cases, these can be substituted with hydroxyl, halogen, such as chlorine or bromine, methoxy or ethoxy.
  • Z 1 can mean alkenyl having up to 4 carbon atoms.
  • Z 1 is aryl or aryloxy, in particular phenyl or phenoxy, alkylmercapto having 1 to 5 carbon atoms or arylmercapto, in particular phenylmercapto, these radicals can be further substituted by hydroxyl, chlorine, cyano, nitro or methoxy.
  • halogen preferably chlorine or bromine, cyano or carbalkoxy with 2 to 5 carbon atoms and especially methoxy.
  • Z 1 also represents those atoms to form a ring together with Y 1 .
  • 5- or in particular 6-membered rings are preferred. They can optionally contain an oxygen atom as a further heteroatom.
  • Substituents on these rings can be hydroxyl, methyl, ethyl, methoxy, chlorine, aryl or carbmethoxy. Of these substituents, methyl and ethyl are particularly suitable.
  • the substituent D 1 forms the residue of a homo- or heterocyclic diazo component, which can be, for example, thienyl, thiazolyl, isothiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, benzothiazolyl, benzisothiazolyl, pyrazolyl, imidazolyl, 1,2, 3-thiazolyl, 1,2,4-triazolyl or phenyl.
  • a homo- or heterocyclic diazo component which can be, for example, thienyl, thiazolyl, isothiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, benzothiazolyl, benzisothiazolyl, pyrazolyl, imidazolyl, 1,2, 3-thiazolyl, 1,2,4-triazolyl or phenyl.
  • Each of these systems can have further substituents on one or more of its carbon atoms and on one or more of its nitrogen atoms, such as alkyl or alkoxy each having 1 to 4 carbon atoms, such as —C 2 H 4 OC 6 H 5 , cycloalkyl with 5 or 6 carbon atoms, Phenyl, electronegative groups such as halogen, especially chlorine or bromine, trifluoromethyl, cyano, nitro, (carboxylic acid) acyl, acetyl, benzoyl, carbalkoxy with 2 to 5 carbon atoms, especially carbmethoxy or carbethoxy, carbalkoxyethoxy with 1 to 4 carbons Substance atoms in the alkoxy part, alkyl sulfone with 1 to 5 carbon atoms, phenyl sulfone, N-alkyl- or N, N-dialkyl-substituted sulfonamido each with 1 to 4 carbon atoms in the alkyl
  • Two adjacent substituents of the ring systems mentioned, preferably para with meta substituents, can together form further fused rings, for example saturated 5-membered rings, benzo rings or cyclic imides, in which the nitrogen atom is optionally with alkoxyalkyl with 1 to 4 carbon atoms in the alkoxy and alkyl part is substituted.
  • D 1 is phenyl, which is substituted with a maximum of 4, optionally different, substituents from the above list.
  • substituents from the above list.
  • electronegatives are preferred. These can be cyano, nitro, chlorine, trifluoromethyl, bromine, acetyl, benzoyl, carbmethoxy, carbethoxy, methoxy, ethoxy or vinyl substituted with cyano and / or carbethoxy or also methyl or ethyl.
  • the electronegative substituents preferably occupy ortho and para positions in the phenyl ring.
  • Valuable azo dyes of the formula (2) are those of the formula wherein X3 and X4 independently of one another optionally substituted with hydroxyl, alkoxy with 1 to 4 carbon atoms, cyano, fluorine, chlorine or bromine alkyl with 1 to 18 carbon atoms, alkenyl with 2 to 4 carbon atoms, cycloalkyl with 5 or 6 carbon atoms, aryl or aralkyl with 1 to 4 carbon atoms in the alkyl part, Y 3 is hydrogen, optionally substituted alkyl having 1 to 8 carbon atoms, alkenyl having 2 to 4 carbon atoms or optionally substituted aryl, or together with Y 1 is used to complete an optionally substituted 5- or 6-membered ring represents necessary atoms, Z 2 represents hydrogen, optionally substituted alkyl having 1 to 4 carbon atoms, optionally substituted alkoxy having 1 to 5 carbon atoms, aryl or aryloxy, alkyl mercapto having 1 to
  • Suitable compounds of the formula (3) are the compounds of the formula wherein X 5 and X 6 independently of one another are optionally substituted by hydroxyl, methoxy, ethoxy, cyano, fluorine, chlorine or bromine alkyl having 1 to 12 carbon atoms or phenyl or benzyl, Y 4 is hydrogen, optionally substituted alkyl having 1 to 8 carbon atoms or optionally substituted Aryl or, together with Y 1, represents the atoms necessary to complete an optionally substituted, saturated 5-membered ring, Z 3 is hydrogen, optionally substituted alkyl having 1 to 4 carbon atoms, optionally substituted alkoxy having 1 to 5 carbon atoms, halogen, cyano, carbalkoxy with 2 to 5 carbon atoms or those atoms, in order to form together with Y 1 an optionally substituted, optionally containing a further heteroatom, 5- or 6-membered ring, D 3 optionally substituted thienyl, thiazolyl, isothi
  • Y 5 hydrogen or alkyl with 1 to 4 carbon atoms optionally substituted with alkoxy with 1 to 4 carbon atoms Y 6 hydrogen, optionally with methoxy, phenyl, hydroxyl, fluorine, chlorine, bromine, carbalkoxy with 1 to 6 carbon atoms in the alkoxy part, acyloxy with 2 ' to 7 carbon atoms or cyano substituted alkyl having 1 to 8 carbon atoms or aryl substituted by alkyl or alkoxy each having 1 to 5 carbon atoms or chlorine or together with Y represents the atoms necessary to complete an optionally substituted, saturated 5-membered ring, Z 4 hydrogen, alkyl or alkoxy each with 1 to 4 carbon atoms, alkoxy substituted with methoxy or ethoxy with 1 or 2 carbon atoms, chlorine, bromine or cyano, carbalkoxy with 2 to 5 carbon atoms or those atoms, together with Y 1 to form a
  • Particularly suitable compounds correspond to the formula wherein D 5 is optionally substituted phenyl and X 5 , X 6 , Y 5 , Y 6 and Z 5 have the meaning given above.
  • a 3 and A 4 are independently hydrogen, alkyl with 1 to 4 carbon atoms, carbalkoxy with 2 to 5 carbon atoms, carbalkoxyethoxy with 1 to 4 carbon atoms in the alkoxy part, trifluoromethyl, cyano, nitro, alkyl sulfone with 1 to 5 carbon atoms or halogen, B 2 Hydrogen optionally substituted with electronegative groups alkyl with 1 to 4 carbon atoms, alkoxy with 1 or 2 carbon atoms, optionally substituted with electronegative groups alkenyl with 2 to 4 carbon atoms, T 2 -CO-, wherein T 2 is methyl or phenyl, carbalkoxy with 2 to 5 carbon atoms, alkyl sulfone with 1 to 6 carbon atoms, phenyl sulfone, N-alkyl- or N, N-dialkyl-substituted sulfonamide, each with 1 or 2 carbon atoms in
  • a 5 and A 6 are hydrogen, methyl, trifluoromethyl, cyano, nitro or halogen
  • E 2 is hydrogen, methyl, carbalkoxy with 2 to 5 carbon atoms, trifluoromethyl, nitro or chlorine
  • X 7 , X 8 , Y 5 , Y 7 , Z 6 and B 3 have the meanings given above.
  • the compounds of the formula (1) in which X 1 , X 2 , Y 1 , Y 2 , Z 1 and D 1 have the meaning given above are prepared by coupling a compound of the formula wherein D 1 has the meaning given above and X ⁇ is an anion, with an N-phenylphosphoramic acid diester of the formula wherein X 1 , X 2 , Y 1 , Y 2 and Z 1 have the meaning given above, in acidic to neutral medium.
  • N-phenylphosphoramic acid diesters of formula (18) are prepared by using an amine of formula wherein Y 1 , Y 2 and Z 1 have the meaning given above, with a phosphoric acid ester chloride of the formula in the presence of a base, or with a phosphite of the formula In which X 1 and X 2 have the meaning given above, in the presence of a base and carbon tetrachloride. The latter method of manufacture is the preferred.
  • phosphites of formula (21) e.g. used are: dimethyl phosphite, diethyl phosphite, diisopropyl phosphite, dibutyl-: phosphite, phenyldodecylphosphite, phenylneopentylphosphite, diethylphosphite, bis 2-ethylhexylphosphite, diphenylphosphite, 2-ethylhexylphosphite, ethylethyl-2,2-isopropylphosphite, isopropyl-S-methylphenyl) phosphite, ethyl 2-isopropyl-5-methylphenyl phosphite, dibenzyl phosphite or ethyl methyl phosphite.
  • chlorides of formula (20) e.g. are used: phosphoric acid diethyl chloride, phosphoric acid dimethyl ester chloride, phosphoric acid dipropylester chloride, phosphoric acid bis (2,2,2-trifluoroethyl) ester chloride.
  • N-phenylphosphoramic acid diesters of the formula (17) are:
  • the radicals D 1 of the formula (17) come predominantly from the benzene or heterocyclic series. eg the thiophene, thiazole-thiadiazole, benzothiazole, benzisothiazole, triazole, pyrazole or indazole series.
  • the following radicals, which correspond to the general formula D 1 -NH 2 may be mentioned individually:
  • the dyes of formula (1) can be used for various purposes. They are suitable e.g. for printing or dyeing textile materials such as polyester or polyester blends according to e.g. the exhaust, padding or thermosol process.
  • polyester fiber material especially textile material, e.g. to mention those made from cellulose ester fibers, such as cellulose 2 1/2 acetate fibers and triacetate fibers, and particularly linear polyester fibers.
  • Linear polyester fibers are to be understood as synthetic fibers which e.g. can be obtained by condensation of terephthalic acid with ethylene glycol or of isophthalic acid or terephthalic acid with 1,4-bis (hydroxymethyl) cyclohexane, and also copolymers of terephthalic and isophthalic acid and ethylene glycol.
  • the linear polyester used so far almost exclusively in the textile industry consists of terephthalic acid and ethylene glycol.
  • the fiber materials can also be used as a mixed fabric among themselves or with other fibers, e.g. Mixtures of polyacrylonitrile polyester, polyamide / polyester, polyester / cotton, polyester / viscose and polyester / wool can be used.
  • the textile material to be dyed can be in various stages of processing. Examples include: loose material, piece goods, such as knitted or woven fabrics, or yarn in the form of a wrap or muff.
  • Mixtures of the azo dyes according to the invention can also be used.
  • the azo dyes according to the invention are also particularly suitable for the production of level mixed tone dyeings, including a dichromy or trichromatic dyeing.
  • Trichromatic is primarily understood to mean a three-way combination of the basic colors yellow (or orange), red and blue.
  • the amount of dyes to be added to the liquor depends on the desired color strength; In general, amounts of 0.001 to 10, preferably 0.001 to 5 percent by weight, based on the textile material used, have proven successful.
  • the liquors can be known carriers based on e.g. Di- or trichlorobenzene, methyl- or ethylbenzene, o-phenylphenol, benzylphenol, diphenyl ether, chlorodiphenyl, methyldiphenyl, cyclohexanone, acetophenone, alkylphenoxyethanol, mono-, di- or trichlorophenoxyethanol or -propanol, pentachlorophenyl-based benzene, especially Contain methyl diphenyl ether, dibenzyl ether, methyl benzoate, butyl benzoate or phenyl benzoate.
  • the carriers are preferably used in an amount of 0.5 g to 2 g / l of liquor or 10 to 60 percent by weight, based on the auxiliary preparation.
  • the dyebaths can contain, in addition to the dyes and the auxiliary according to the invention, also oligomer inhibitors, anti-foaming agents, wrinkle-free agents and preferably dispersants.
  • the dispersants are used primarily to achieve a good fine distribution of the disperse dyes.
  • the dispersants which are generally used for dyeing with disperse dyes can be used.
  • Suitable dispersants are, for example, anionic surfactants, which can be present alone or as mixtures.
  • Lignin sulfonates polyphosphates and preferably formaldehyde condensation products of aromatic sulfonic acids, formaldehyde and optionally mono- or bifunctional phenols, such as e.g. from cresol, ⁇ -naphtholsulfonic acid and formaldehyde, from benzenesulfonic acid, formaldehyde and naphthalenesulfonic acid, from naphthalenesulfonic acid and formaldehyde or from naphthalenesulfonic acid, dihydroxydiphenyl sulfone and formaldehyde.
  • cresol cresol
  • ⁇ -naphtholsulfonic acid and formaldehyde from benzenesulfonic acid, formaldehyde and naphthalenesulfonic acid, from naphthalenesulfonic acid and formaldehyde or from naphthalenesulfonic acid, dihydroxydipheny
  • the disodium salt of di- (6-sulfonaphthyl-2-) methane is preferred.
  • anionic dispersants can also be used.
  • the anionic dispersants are normally in the form of their alkali metal salts, ammonium salts or amine salts.
  • These dispersants are preferably used in an amount of 0.1 to 5 g / l of liquor.
  • the dyeings are advantageously carried out from an aqueous liquor using the exhaust process.
  • the liquor ratio can accordingly be chosen within a wide range, e.g. 1: 4 to 1: 100, preferably 1:10 to 1:50.
  • the temperature at which dyeing is carried out is at least 70 ° C and generally it is not higher than 140 ° C. It is preferably in the range from 80 to 135 ° C.
  • the heat setting with a dye liquor containing this azo dye according to the invention is carried out in a temperature range from 100 to 220 ° C. after the fabric has previously been dried at approximately 100 ° C.
  • Linear polyester fibers and cellulose triacetate fibers are preferably dyed by the so-called high-temperature process in closed. sen and expediently also pressure-resistant apparatus at temperatures of at least 100 ° C, preferably between 100 and 135 ° C, and possibly under pressure. Circulation apparatuses such as cross-wound or tree dyeing machines, reel runners, nozzle or drum dyeing machines, muff dyeing machines, paddles or jiggers are suitable as closed vessels.
  • the azo dyes according to the invention can also be incorporated into the printing pastes which are usually used for printing polyester or polyester blend fabrics.
  • the azo dyes according to the invention are particularly advantageously suitable as image dyes for the silver color bleaching process. Accordingly, it is possible to produce valuable photographic materials, in particular silver color bleaching materials, which contain at least one layer with a dye of the formula (1) on a support in a conventional manner known per se.
  • a transparent, metallic-reflective or, preferably, white-opaque material which cannot absorb any liquid from the baths can be used as the support for the silver halide emulsion layers.
  • the carrier can consist, for example, of pigmented cellulose triacetate or polyester. If it is made of paper felt, it must be coated on both sides or coated with polyethylene.
  • the light-sensitive layers are located on at least one side of this support, preferably in the known arrangement, d4h. a red-sensitized silver halide emulsion layer containing a blue-green azo dye on the bottom, a green-sensitized silver halide emulsion layer containing a purple azo dye above and a blue-sensitive silver halide emulsion layer containing a yellow azo dye above.
  • the material can also be sub-layers, Contain intermediate layers, filter layers and protective layers, but the total thickness of the layers should generally not exceed 20 u.
  • the dyes according to the invention are lipophilic and are generally incorporated into the gelatin as solutions in high-boiling solvents.
  • Forming dyes may be applicable as a solution in such a solvent, with the aid of a readily volatile auxiliary solvent at normal or slightly elevated temperature to add to an aqueous gelatin solution with good stirring - in most cases it is sufficient to ver.
  • the mixture is then brought together with a gelatin containing silver halide and / or other materials for producing photographic images, cast onto a base in a conventional manner to form a layer and optionally dried.
  • Dyes of formula (1) dissolved in organic solvents can be added directly to a gelatin containing silver halide and / or other materials for producing photographic images. So it is e.g. possible to add the dye solution just before pouring.
  • the casting solution can also contain other additives such as hardening agents, sequestering agents and wetting agents, as well as sensitizers and stabilizers for the silver halide.
  • the dyes do not undergo chemical reactions with the light-sensitive materials.
  • the dyes of the formula (1) are very diffusion-resistant because they form stable, organic solutions. They are insensitive to calcium ions and bleachable well on white.
  • the dyes When added to the casting solutions, the dyes produce neither an increase in viscosity nor a significant change in viscosity when the casting mixture is left to stand.
  • the spectral absorption in gelatin is such that, depending on the structure, the dyes of the formula (1) can be combined to form a triple dye composed of a yellow, purple or cyan dye which has gray tones that appear neutral to the eye over the entire density range having.
  • the photographic silver color bleaching material containing the dyes of the formula (1) is distinguished in particular by brilliant colors, good color rendering and excellent light fastness.
  • An important characteristic of a good color copy material is an optimal tone reproduction and balanced color gradations in all density ranges. It is always difficult to control the color balance, since different bleaching behavior of the azo dyes cannot always be compensated for with the conventional methods of material build-up, such as sensitivity and contrast of the silver emulsions used. As a result, the selection of the image dyes and, in particular, that of the processing components in the Bleaching bath restricted.
  • the latent silver image created during exposure is developed.
  • the image dye assigned to the silver is bleached out in accordance with the image-based distribution of the silver.
  • the third step is necessary to reoxidize the excess image silver that is still present after the color bleaching.
  • the silver, which is now entirely in the form of halides is removed by leaching out with a complexing agent, in particular a salt of thiosulfuric acid, in order to render the finished image insensitive to further exposure and to clear the pure color image of cloudiness.
  • the second process step takes place in the usual known processes in a strongly acidic medium, a catalyst being added to accelerate the color bleaching.
  • the bleach baths also contain a silver complexing agent or ligand. Both components, catalyst and ligand, are necessary in order to transfer the reducing effect of the metallic, non-diffusible image silver to the non-diffusible dye.
  • the resulting silver image by reduction of the reduced form of the catalyst serves as an intermediate carrier which, after covering a certain diffusion - stretch, the dye is irreversibly reduced and thus bleached, and is itself reoxidized to its original form.
  • the property of the reduced stage of the bleaching catalyst to freely diffuse between image silver and dye to be bleached makes it possible to spatially separate silver and image dye to a certain extent, i.e. That is, to arrange the bleachable dye and the silver halide emulsion assigned to it not or only partially in the same layer but in adjacent layers.
  • Such silver color bleaching materials are e.g. in DE-A-2 036 918, 2 132 835 and 2 132 836.
  • the combined color and silver bleaching baths (preparations) for processing the exposed silver color bleaching material contain components (a) to (e) and optionally (f): (a) strong acid, (b) water-soluble iodide, (c) water-soluble oxidizing agent, ( d) antioxidants, (e) bleach catalysts, (f) bleach accelerators.
  • the amount of bleaching catalysts used in the preferably aqueous treatment baths can vary within wide limits and is approximately 0.05 to 10 g / l of bleaching bath.
  • the temperature of the bleaching bath is generally between 20 and 90 ° C., preferably between 20 and 60 ° C., the processing time required, of course, being shorter at a higher temperature than at a lower temperature.
  • the bleaching baths are stable within the specified temperature range.
  • the aqueous bleaching preparations required for processing are in in the form of dilute aqueous solutions containing the components mentioned.
  • other methods are also conceivable, for example the use in paste form.
  • the aqueous bleaching preparation according to the present invention can e.g. be produced from liquid, in particular aqueous concentrates of individual or all components ((a) to (f)).
  • aqueous concentrates of individual or all components ((a) to (f)).
  • one uses e.g. two liquid concentrates, one of which contains the strong acid (a) and the oxidizing agent (c) and the other of which contains the other components (b), (d), (e) and optionally (f), the latter concentrating to improve solubility , in particular component (e), an additional solvent such as ethyl, propyl or benzyl alcohol, ethylene glycol methyl or ethyl ether can be added.
  • an additional solvent such as ethyl, propyl or benzyl alcohol, ethylene glycol methyl or ethyl ether can be added.
  • the combined F can ARB and silver bleach baths contain alkyl or aryl sulfonic acids and, in particular p-toluenesulfonic acid, sulfuric acid, sulfamic acid or trichloroacetic acid. If necessary, mixtures of these acids can also be used.
  • the pH value of the bleach bath is normally not more than 2 and preferably not more than 1.
  • the water-soluble iodides are generally alkali metal iodides, especially sodium and potassium iodide.
  • oxidizing agent (c) Water-soluble aromatic mononitro and dinitro compounds and anthraquinone sulfonic acid derivatives are expediently used as the oxidizing agent (c).
  • the use of such oxidizing agents serves to influence the color balance and the contrast of the images produced in the color bleaching process and is known from German patent specification 735 672, British patent specifications 539 190 and 539 509 and Japanese patent publication 22673/69.
  • the compounds of component (c) serve to flatten the gradation.
  • Reductones or water-soluble mercapto compounds are advantageously used as antioxidants (anticorrosive agents (d)).
  • Suitable reductones are, in particular, aci reductones with a 3-carbonylenediol (1,2) grouping, such as reductin, triose reductone or preferably ascorbic acid.
  • Examples of mercapto compounds are thioglycerin, but especially the compounds of the formula or preferably into consideration, in which q is an integer from 2 to 12, B is a sulfonic acid or carboxylic acid group and m is one of the numbers 3 and 4.
  • Mercapto compounds which can be used as antioxidants are described in DE-A-2 258 076 and DE-A-2 423 814.
  • Suitable further antioxidants are alkali metal, alkaline earth metal or ammonium bisulfite adducts of organic carbonyl compounds, preferably alkali metal or ammonium bisulfite adducts of monoaldehydes with 1 to 4 or dialdehydes with 2 to 5 carbon atoms (DE-A-2 737 142).
  • Examples include the particularly preferred formaldehyde bisulfite adduct and the corresponding adducts of acetaldehyde, propionaldehyde, butyraldehyde or isobutyraldehyde, of glyoxal, malondialdehyde or glutardialdehyde.
  • the tertiary water-soluble phosphines mentioned below as bleach accelerators can also be used simultaneously as antioxidants.
  • Further bleach accelerators are the water-soluble tertiary phosphines known from DE-OS 2 651 969, which preferably contain at least one cyanoethyl group.
  • Preferred tertiary phosphines correspond to the formula wherein X 1 -CH 2 CH 2 CN or - (CH 2 ) 2 OCH 3 , Y 1 - (CH 2 ) 2 SO 3 ⁇ M ⁇ , - (CH 2 ) 3 -SO 3 ⁇ M ⁇ , - (CH 2 ) 4 ⁇ M ⁇ , - (CH 2 ) 2 OCH 3 or -CH 2 N (C 2 H 5 ) 2 , W 1 -CH 2 CH 2 CN or phenyl and M is a cation, in particular an alkali metal cation, for example the sodium or is potassium cation.
  • All baths can contain other common additives such as Contain hardening agents, wetting agents, optical brighteners or UV protection agents.
  • Baths of conventional composition can be used for silver development, e.g. those which contain hydroquinone as the developer and optionally additionally 1-phenyl-3-pyrazolidinone. If appropriate, the silver detergent bath already contains a bleaching catalyst.
  • the silver fixing bath can be composed in a known and customary manner.
  • the fixative used is e.g. Sodium thiosulfate or advantageously ammonium thiosulfate, if desired with additives such as sodium bisulfite and / or sodium metabisulfite.
  • the precipitate is filtered off and recrystallized in an acetonitrile-water mixture.
  • the red-violet intermediate of the formula is dissolved in .10 ml of N-methyl-pyrrolidone in the presence of 0.2 g of copper (I) cyanide.
  • the mixture is stirred under nitrogen for 60 minutes and finally poured into 100 ml of ice water.
  • the precipitate is filtered off and dissolved in methylene chloride.
  • the solution obtained is washed twice with 40% ammonium rhodanide solution, then once with sodium mercaptopropionate solution, once with sodium bicarbonate solution and finally with water.
  • the solution is dried over magnesium sulfate and the solvent is evaporated off.
  • the orange-colored intermediate of the formula is dissolved in 12 ml of N-methyl-pyrrolidone. 0.4 g of copper (I) cyanide are added. The mixture is stirred under nitrogen for 16 hours and finally discharged into water. The precipitate is filtered off and dissolved in methylene chloride. The solution obtained is washed twice with 40% ammonium rhodanide solution, then once with sodium mercaptopropionate solution, once with sodium bicarbonate solution and finally with water.
  • the solution is dried over magnesium sulfate and the solvent is evaporated.
  • 11 mg of dye of the formula are dissolved in 2 ml of a mixture of ethyl acetate and tricresyl phosphate (mixing ratio 9: 1). This solution is added to a mixture of 6.6 ml of 6% gelatin solution and 1.4 ml of 3% Iger solution of dibutylnaphthalenesulfonic acid. The entire mixture is emulsified with ultrasound. 2.5 ml of this dye emulsion are mixed with 2 ml of 4% gelatin solution, 5 ml of water, ml of 1% hardener solution and 0.5 ml of a silver iodide gelatin emulsion which contains about 22 g of silver per kg of gelatin.
  • the bleach bath contains the following components: In this way you get a brilliant, lightfast, blue-green wedge. At the point of originally maximum silver densities, the dye is completely bleached to white.
  • Example 4 An opaque triacetate support is coated in accordance with Example 4, but the silver halide gelatin emulsion contains 16 mg of dye of the formula After exposure and processing of the material in the manner described in Example 4, a brilliant, purple-colored wedge of high light fastness is obtained.
  • Example 4 If an opaque triacetate support according to Example 4 is coated with a silver halide emulsion containing 37 mg of the dye of the formula contains, exposed and processed in the manner described in Example 4, a brilliant, yellow wedge of high light fastness is obtained.
  • the developer bath has the following composition per liter of solution:
  • the silver color bleach bath has the following composition per liter of solution:
  • the fixer contains per liter of solution:
  • a brilliant, lightfast purple wedge is obtained, which is completely bleached on white at the places of the original greatest silver density.
  • 1 part of the dye of the formula is wet-ground with 2 parts of a 50% aqueous solution of the sodium salt of dinaphthylmethane disulfonic acid and dried.
  • This dye preparation is stirred with 40 parts of a 10% aqueous solution of the sodium salt of N-butyl- ⁇ -heptadecylbenzimidazole disulfonic acid and 4 parts of a 40% acetic acid solution are added.
  • a dye bath of 4000 parts is prepared from this by dilution with water.
  • the mixture is stirred until the dye has completely dispersed and then polyethylene glycol terephthalate fabric is printed with this paste.
  • the fabric is dried and steamed at 1 1/2 atm for 20 minutes, rinsed with cold water for 10 minutes, soaped twice hot with the addition of a little hydrosulfite, rinsed cold and dried. You get a real blue-red print.
  • 10 g of a diol fabric (PES) is now dyed as follows: The fabric is taken into the dyeing liquor at 70 ° C. and the temperature of the liquor is increased to 100 ° C. over 30 minutes. At this temperature you dye for 90 minutes.
  • the dyeing obtained is rinsed hot and cold, reductively cleaned with sodium hydrosulfite, rinsed again and dried.
  • 20 g / l finely dispersed dye of the formula are homogenized in 200 g / 1 sodium alginate thickener 2.5% and 2 g / l of the sodium salt of dibutylnaphthalenesulfonic acid (wetting agent).
  • a diol fabric is padded with this dipping liquor with a squeezing effect of 65%, dried at 100 ° C. for 2 minutes and heat-set at 210 ° C. for 60 seconds. After rinsing, reductive cleaning and drying, a strong bluish red color is obtained with good lightfastness.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Coloring (AREA)
  • Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
EP81810154A 1980-04-30 1981-04-24 Colorants azoiques, procédé pour leur préparation et leur utilisation dans les matériaux photographiques en couleurs pour le procédé de blanchiment à l'argent Expired EP0040171B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH334180 1980-04-30
CH3341/80 1980-04-30

Publications (3)

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EP0040171A2 true EP0040171A2 (fr) 1981-11-18
EP0040171A3 EP0040171A3 (en) 1981-11-25
EP0040171B1 EP0040171B1 (fr) 1984-03-21

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Country Status (4)

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US (2) US4409143A (fr)
EP (1) EP0040171B1 (fr)
JP (1) JPS5728161A (fr)
DE (1) DE3162755D1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0149978A2 (fr) * 1984-01-20 1985-07-31 Ilford Ag Procédé pour la réalisation d'images photographiques par le procédé de blanchiment des couleurs à l'argent
EP0169813A2 (fr) * 1984-07-27 1986-01-29 Ciba-Geigy Ag Matériau d'enregistrement photographique pour le procédé de blanchiment des couleurs à l'argent
EP0233152A2 (fr) * 1986-02-11 1987-08-19 Ilford Ag Matériau photographique pour le blanchiment des couleurs à l'argent
WO2004072184A1 (fr) * 2003-02-13 2004-08-26 Lanxess Deutschland Gmbh Complexes metalliques servant de composes photoabsorbants dans la couche d'information de supports de donnees optiques

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2286795A (en) * 1941-08-22 1942-06-16 Eastman Kodak Co Azo compounds and material colored therewith

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2328570A (en) * 1938-08-16 1943-09-07 Eastman Kodak Co Azo compounds and material colored therewith
US2200543A (en) * 1939-08-25 1940-05-14 Eastman Kodak Co Azo compounds and material colored therewith
US2638478A (en) * 1949-05-04 1953-05-12 Hoffmann La Roche Phosphorus-containing derivatives of m-amino-phenols
US4026709A (en) * 1973-03-09 1977-05-31 Ciba-Geigy Ag Color photographic recording material
DE3161758D1 (en) * 1980-04-30 1984-02-02 Ciba Geigy Ag Colour photopgraphic material for the silver-dye bleaching process, process for the production of this material and its use in the production of photographic images
US4346155A (en) * 1980-08-01 1982-08-24 Eastman Kodak Company Photographic products and processes employing novel nondiffusible 6-arylazo-3-pyridinol magenta dye-releasing compounds and percursors thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2286795A (en) * 1941-08-22 1942-06-16 Eastman Kodak Co Azo compounds and material colored therewith

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0149978A2 (fr) * 1984-01-20 1985-07-31 Ilford Ag Procédé pour la réalisation d'images photographiques par le procédé de blanchiment des couleurs à l'argent
EP0149978A3 (en) * 1984-01-20 1988-08-31 Ciba-Geigy Ag Process for the production of photographic images by the silver dye-bleaching process
EP0169813A2 (fr) * 1984-07-27 1986-01-29 Ciba-Geigy Ag Matériau d'enregistrement photographique pour le procédé de blanchiment des couleurs à l'argent
EP0169813A3 (en) * 1984-07-27 1989-01-11 Ciba-Geigy Ag Photographic recording material for the silver dye-bleaching process
EP0233152A2 (fr) * 1986-02-11 1987-08-19 Ilford Ag Matériau photographique pour le blanchiment des couleurs à l'argent
EP0233152A3 (en) * 1986-02-11 1988-08-24 Ciba-Geigy Ag Photographic material for the silver-dye bleaching process
WO2004072184A1 (fr) * 2003-02-13 2004-08-26 Lanxess Deutschland Gmbh Complexes metalliques servant de composes photoabsorbants dans la couche d'information de supports de donnees optiques

Also Published As

Publication number Publication date
JPS5728161A (en) 1982-02-15
EP0040171A3 (en) 1981-11-25
US4456668A (en) 1984-06-26
JPH0222106B2 (fr) 1990-05-17
EP0040171B1 (fr) 1984-03-21
US4409143A (en) 1983-10-11
DE3162755D1 (en) 1984-04-26

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